According to the crystallographic structures, the stainless steels can be categorized into the austenitic type, the martensitic type, and the ferritic type. Stainless steels have superior corrosion resistance and are suitable to be used in structures or decorative surfaces, such as screws, nuts, shafts, pins, decorative accessories, and the casings of watches, mobile phones, electronic products and electric appliances. However, the surface mechanical properties of the traditional stainless steels are usually unable to meet application requirements. For example, 316L stainless steel, a designation of AISI (American Iron and Steel Institute), contains 15-18 wt % Cr, 12-15 wt % Ni, 2-3 wt % Mo, and the balance of iron and impurities. 316L stainless steel has a hardness of HRB50-70, and the surface thereof is likely to be damaged by abrasion or collision.
A nitriding method or a carburizing method is usually used to increase the concentration of carbon or generate nitride in the surface of a stainless steel workpiece so as to promote the surface mechanical properties. The carburizing method is particularly extensively used in the industry. Normally, stainless steel is carburized in a carbon-bearing atmosphere at a specified temperature for a long time. Thereby, carbon atoms can implant into the surface of a workpiece to form a carburized layer. In a U.S. Pat. No. 7,468,107, a stainless steel workpiece is carburized in a methane-bearing atmosphere at a temperature of 1,900-2,000° F. At such a high temperature (over 980° C.), the chromium in stainless steels is likely to react with carbon in the atmosphere. Thus, the amount of dissolved chromium in the surface of the stainless steel workpiece decreases, and the corrosion resistance of the stainless steel workpiece is degraded. Accordingly, the carburizing temperature of 316L stainless steel workpiece is preferred to be below the temperature of the nose in the continuous cooling transformation (CCT) diagram shown in FIG. 1.
The surface of the stainless steel workpiece usually has a passivation layer hindering implantation of carbon atoms and impairing formation of a carburized layer when carburization is undertaken at a temperature below the nose temperature. Therefore, the passivation layer should be removed before low-temperature carburization. U.S. Pat. Nos. 5,792,282, 5,556,483, and 5,593,510 disclosed a carburization method for austenitic stainless steel, wherein stainless steel is placed in a fluorine- or fluoride-bearing atmosphere at a temperature of 250-450° C. for tens of minutes to convert the passivation layer into a fluorinated layer. Next, stainless steel is carburized at a temperature of 400-500° C. Carbon atoms can more easily pass through the fluorinated layer than the passivation layer containing chromium oxide. Thus, the carburized depth may reach about 20 μm, and the hardness may reach about HV800, in the abovementioned prior arts.
A U.S. Pat. No. 6,547,888 disclosed modified low temperature case hardening processes, wherein stainless steel is placed in an N2 atmosphere containing 20 vol % HCl at a temperature of 550° F. for 60 minutes to activate the passivation layer. Then, the stainless steel is carburized at a temperature of 880-980° F. In addition, U.S. Pat. Nos. 6,461,448 and 6,093,303 disclosed other low temperature case hardening processes, wherein stainless steel is placed in a fusion salt bath containing a mixture of a cyanide salt, a metal halide salt and calcium carbide, wherein the cyanide salt and the metal halide salt are used to activate the passivation layer of stainless steel, and wherein calcium carbide is the carbon source for carburization.
In the abovementioned prior arts, all the gases and salt baths have halides, which are not only expensive but also harmful to human bodies and the environment. Thus, carburization is likely to cause safety problems. Further, halides may corrode piping and equipment and induce stress corrosion cracking. Therefore, the abovementioned methods are unsuitable for industrial application.